This invention relates to the catalyzed preparation and reactions of a reactive, low molecular weight, viscous, essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin) prepared employing a catalyst comprising a Periodic Group IVb metallocene and an aluminoxane, and more particularly to the catalyzed preparation and reactions of a reactive, low molecular weight, viscous essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin) prepared from a feed stock containing one or more C.sub.3 to C.sub.20 1-olefin and other volatile hydrocarbon liquids. The viscous polymers of this invention are essentially terminally-unsaturated poly(1-olefin)s or copoly(1-olefin)s with such terminal unsaturation being more than 80% vinylidene type made by a catalyst system using a Periodic Group IVb metallocene and an aluminoxane.
A number of patents and other publications have described the use of transition element, including those of Periodic Group IVb, metallocene/aluminoxane catalysts (supported or unsupported) for the polymerization of 1-olefins and certain cycloalkenes such as ethylene, propylene, butene1, hexene-1, octene-1, styrene, cyclobutene, cyclopentene, and norbornene. The catalysts are said to have advantages which include increased polymerization activity, the ability to produce some terminal unsaturation and a narrow molecular weight distribution in the product polymer, and the ability to precisely choose polymer stereo regularity. See U.S. Pat. Nos. 4,530,914; 4,752,597; 4,808,561; and 5,001,244. See also U.S. Pat. No. 4,542,199 where polymerization of olefins of formula CH.sub.2 CHR in which R is H or C.sub.1 to C.sub.10 alkyl is described, the Periodic Group IVb metallocene employed is a bis(cyclopentadienyl) transition element particularly zirconium, and copolymerization with alpha-omega dienes is taught. In Example 4 of that patent, bis(cyclopentadienyl)zirconium dichloride and aluminoxane are used to give atactic polypropylene of molecular weight 5000.
Typically, a high ratio of methylaluminoxane(MAO) cocatalyst to metallocene must be used (approximately 300/1 or more). But see U.S. Pat. No. 4,808,561 wherein the reaction product of a mixture of metallocene and aluminoxane in the presence of a support is said to produce a catalyst which will polymerize olefins at an acceptable rate without the presence of an objectional excess of aluminum.
Also, see U.S. Pat. No. 4,752,597 which describes the use of a solid reaction product of a transition metal metallocene, particularly a Group IVb metallocene, with aluminoxane cocatalyst to effectively polymerize olefin wherein the molar ratio of metallocene to aluminoxane lies between 1:12 and 1:100. It has also been reported in U.S. Pat. No. 5,001,244 that the addition of a boron compound such as tris(perfluorophenyl)boron is able to reduce or eliminate the need for such a high aluminum to metallocene ratio.
In U.S. Pat. No. 5,162,466, use of a cyclo(pentadienyl)dicarbollide complexes of titanium, zirconium and hafnium as catalyst in the absence of a cocatalyst, such as an aluminoxane, is taught for polymerization of ethylene or copolymerization of ethylene with a C.sub.3 to C.sub.8 alpha olefin.
Stanford Research Institute reports that the use of one of these metallocene Ziegler catalysts to make polyethylene is being commercialized and the process is described as capable of preparing linear low density polyethylenes of superior physical properties.
It is reported by W. Kaminsky et al. in Bull. Soc. Chim. Belg. 99 (2),103-111(1990) that simple zirconium metallocenes polymerize propylene to atactic polymer. The reference also shows that chiral, ethylene-bridged bis(tetrahydroindenyl)zirconium dichloride and methylaluminoxane catalyst can produce isotactic polypropylene.
See also Polymerization of Propene and Butene with a Chiral Zirconocene and Methylalumoxane as Cocatalyst by W. Kaminsky et al. in Angew. Chem. Int. Ed. Engl. 2 4 No. 6, pp 507-508 (1985). Reisconi et al. in J. Am. Chem. Soc. 114 1025-1032(1992) states that polymerization of propylene with a bis(indenyl)zirconium dichloride (Ind.sub.2 ZrCl.sub.2) and MAO catalyst leads to termination by beta hydrogen elimination and thus a polypropylene product which has some terminal unsaturation of the vinylidene type. In WO 9111488 to Exxon, a copolymeric wax crystal modifier of number average molecular weight between 300 and 15,000 made from ethylene and at least one alpha-olefin and containing at least 40 mol % ethylene is made using a metallocene catalyst. The copolymer has at least 30% of the polymer chains exhibiting terminal ethenylidine unsaturation.
In U.S. Pat. No. 4,658,078 use of (a) cyclo(pentadienyl)zirconium or hafnium metallocene and (b) an aluminoxane catalyst, with atom ratio of Al to Zr or Hf of 1 to 100, is taught for dimerizing a C.sub.3 to C.sub.32 alpha olefin at temperatures between -60.degree. C. and 280.degree. C.
In U.S. Pat. No. 4,704,491 copolymerizing ethylene and a C.sub.3 to C.sub.20 alpha-olefin in the presence of a compound of Periodic Group IVb and an aluminoxane catalyst is taught for making a random copolymer.
In U.S. Pat. No. 5,017,665, use of a supported, bridged bis(indenyl)zirconium dichloride/aluminoxane catalyst is taught for the copolymerization of a mixture of ethylene and 1,4-diene.
In U.S. Pat. No. 5,077,255, copolymerizing ethylene and a C.sub.3 to C.sub.20 alpha-olefin in the presence of a compound of Periodic Group IVb and an aluminoxane catalyst is taught for making a random copolymer having a number average molecular weight above 20,000 and an average of at least 30% of the polymer chains contain terminal ethylidene unsaturation.
In U.S. Pat. No. 5,151,204, use of a supported reaction product of (a) at least one metallocene of a metal of Group IVb, Vb, and VIb, (b) a non-metallocene transition metal containing compound of a Group IVb, Vb, and VIb metal and (c) an aluminoxane catalyst is taught for the copolymerization of a mixture of ethylene and other mono and diolefins.
In Japanese Patent No. 01,132,605 it is reported that a poly(1-olefin) made with bis(cyclopentadienyl)zirconium dichloride and methylaluminoxane can be reacted with perbenzoic acid to form epoxide.
In European Patent Application No. 0 268 214, it is reported that propylene oligomers were made with an alkyl substituted cyclopentadienyl compound of zirconium and/or hafnium and a condensation product of organoaluminum compound and water. In Comparative Examples 1, 2, and 3, however, using three non-substituted cyclopentadienyl compounds, i.e., bis(cyclopentadienyl)zirconium, hafnium, and titanium dichloride, a polymerization of propylene reaction took place preferentially to propylene oliogomerization reaction and products were all high polymers which predominantly had vinylidene group as terminal unsaturated group.
Terminal unsaturation of the vinylidene type can be very important to polymer reactivity in the case of low molecular weight, viscous polybutenes when being functionalized and a number of ways to enhance it have been suggested. For example, use of a BF.sub.3 catalyst can substantially reduce the amount of tri- and tetra-substituted terminal olefin in the polymerization and produce more vinylidene type of termination. Terminal unsaturation of the proper type could also be very helpful to the reactivity of poly(1-olefins).
Now it has been found that a low molecular weight, viscous essentially-1-olefin-containing poly(1-olefin) or copoly(1-olefin) can be formed from a feed stock containing one or more C.sub.3 to C.sub.20 1-olefin and other volatile hydrocarbons by selectively polymerizing the 1-olefins with a Ziegler type metallocene and aluminoxane catalyst. Furthermore, viscous poly(1-olefins) and copoly(1-olefins) so formed are almost completely terminally unsaturated and their terminal unsaturation is, advantageously, largely of the vinylidene type. Such viscous polymers are very reactive because of the presence of the high degree of unsaturation and the extensive vinylidene termination and therefore can be easily functionalized in high yields by conventional methods to make a range of useful products. Products and process are described here in which the terminal olefinic linkage, for example, has been used to alkylate an aromatic ring, or has undergone an Ene reaction, an addition, a hydroformylation, a hydrosilylation, a chlorination, and the like. The lack of polymerization activity of these catalysts towards olefins other than 1-olefins allows a common refinery streams containing a mixture of olefins including isobutylene to be effectively polymerized to make polyisobutene by the usual acid catalyzed process as well as produce the low molecular weight, viscous poly(1-olefin) or copoly(1-olefin) of this invention. This multistep procedure involves a different catalyst for each polymerization and utilizes more fully the components of the refinery stream which after polyisobutylene formation is customarily used for fuel.